Organometallic compounds and processes for preparation thereof

ABSTRACT

This invention relates to organometallic compounds represented by the formula LML′ wherein M is a metal or metalloid, L is a substituted or unsubstituted cyclopentadienyl group or cyclopentadienyl-like group, a substituted or unsubstituted pentadienyl group or pentadienyl-like group, or a substituted or unsubstituted pyrrolyl group or pyrrolyl-like group, and L′ is a substituted or unsubstituted pyrrolyl group or pyrrolyl-like group, a process for producing the organometallic compounds, and a method for producing a film or coating from the organometallic compounds. The organometallic compounds are useful in semiconductor applications as chemical vapor or atomic layer deposition precursors for film depositions.

This application is a divisional of prior U.S. application Ser. No.11/216,043, filed on Sep. 1, 2005, now U.S. Pat. No. 7,619,093 B2.

FIELD OF THE INVENTION

This invention relates to organometallic compounds represented by theformula LML′ wherein M is a metal or metalloid, L is a substituted orunsubstituted cyclopentadienyl group or cyclopentadienyl-like group, asubstituted or unsubstituted pentadienyl group or pentadienyl-likegroup, or a substituted or unsubstituted pyrrolyl group or pyrrolyl-likegroup, and L′ is a substituted or unsubstituted pyrrolyl group orpyrrolyl-like group, a process for producing the organometalliccompounds, and a method for producing a film or coating from theorganometallic compounds.

BACKGROUND OF THE INVENTION

Chemical vapor deposition methods are employed to form films of materialon substrates such as wafers or other surfaces during the manufacture orprocessing of semiconductors. In chemical vapor deposition, a chemicalvapor deposition precursor, also known as a chemical vapor depositionchemical compound, is decomposed thermally, chemically, photochemicallyor by plasma activation, to form a thin film having a desiredcomposition. For instance, a vapor phase chemical vapor depositionprecursor can be contacted with a substrate that is heated to atemperature higher than the decomposition temperature of the precursor,to form a metal or metal oxide film on the substrate. Preferably,chemical vapor deposition precursors are volatile, heat decomposable andcapable of producing uniform films under chemical vapor depositionconditions.

The semiconductor industry is currently considering the use of thinfilms of ruthenium metal for a variety of applications. Manyorganometallic complexes have been evaluated as potential precursors forthe formation of these thin films. These include, for example, carbonylcomplexes such as Ru₃(CO)₁₂, diene complexes such as Ru(η³-C₆H₈)(CO)₃,Ru(η³-C₆H₈)(η⁶-C₆H₆), beta-diketonates such as Ru(DPM)₃, Ru(OD)₃ andruthenocenes such as RuCp₂, Ru(EtCp)₂.

Both the carbonyl and diene complexes tend to exhibit low thermalstabilities which complicates their processing. While thebeta-diketonates are thermally stable at moderate temperatures, theirlow vapor pressures married with their solid state at room temperaturemake it difficult to achieve high growth rates during film deposition.

Ruthenocenes have received considerable attention as precursors for Ruthin film deposition. While ruthenocene is a solid, thefunctionalization of the two cyclopentadienyl ligands with ethylsubstituents yields a liquid precursor that shares the chemicalcharacteristics of the parent ruthenocene. Unfortunately, depositionswith this precursor have generally exhibited long incubation times andpoor nucleation densities.

U.S. Pat. No. 6,605,735 B2 discloses half-sandwich organometallicruthenium compounds that have a cyclopentadienyl and pentadienyl groupbonded to ruthenium. The cyclopentadienyl group can be mono-substitutedor unsubstituted. The pentadienyl group can be mono-, di- ortri-substituted or unsubstituted. Certain substitution patterns arespecifically excluded. It is stated in the patent that the inventorsconducted extensive studies and found that the decomposition temperatureof a ruthenocene can be lowered by substituting one of thecyclopentadienyl rings by linear pentadienyl. By introducing a singlelower alkyl group into the cyclopentadienyl ring, it is stated in thepatent that the half-sandwich organometallic ruthenium compounds havebeen found to be liquid at room temperature and exhibit favorablevaporization and decomposition properties. These compounds are used forproducing a ruthenium-containing thin film by chemical vapor deposition.

In developing methods for forming thin films by chemical vapordeposition or atomic layer deposition methods, a need continues to existfor precursors that preferably are liquid at room temperature, haveadequate vapor pressure, have appropriate thermal stability (i.e., forchemical vapor deposition will decompose on the heated substrate but notduring delivery, and for atomic layer deposition will not decomposethermally but will react when exposed to co-reactant), can form uniformfilms, and will leave behind very little, if any, undesired impurities(e.g., halides, carbon, etc.). Therefore, a need continues to exist fordeveloping new compounds and for exploring their potential as chemicalvapor or atomic layer deposition precursors for film depositions. Itwould therefore be desirable in the art to provide a precursor thatpossesses some, or preferably all, of the above characteristics.

SUMMARY OF THE INVENTION

This invention relates in part to organometallic compounds selected fromthe following:

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ and R₁₁ are the same ordifferent and each represents hydrogen, a halogen atom, an acyl grouphaving from 1 to about 12 carbon atoms, an alkoxy group having from 1 toabout 12 carbon atoms, an alkoxycarbonyl group having from 1 to about 12carbon atoms, an alkyl group having from 1 to about 12 carbon atoms, anamine group having from 1 to about 12 carbon atoms or a silyl grouphaving from 0 to about 12 carbon atoms.

More generally, this invention relates in part to organometalliccompounds represented by the formula LML′ wherein M is a metal ormetalloid, L is a substituted or unsubstituted cyclopentadienyl group, asubstituted or unsubstituted cyclopentadienyl-like group, a substitutedor unsubstituted pentadienyl group, a substituted or unsubstitutedpentadienyl-like group, a substituted or unsubstituted pyrrolyl group ora substituted or unsubstituted pyrrolyl-like group, and L′ is asubstituted or unsubstituted pyrrolyl group or a substituted orunsubstituted pyrrolyl-like group.

This invention also relates in part to a process for the production ofan organometallic compound represented by the formula LML′ wherein M isa metal or metalloid, L is a substituted or unsubstitutedcyclopentadienyl group, a substituted or unsubstitutedcyclopentadienyl-like group, a substituted or unsubstituted pentadienylgroup, a substituted or unsubstituted pentadienyl-like group, asubstituted or unsubstituted pyrrolyl group or a substituted orunsubstituted pyrrolyl-like group, and L′ is a substituted orunsubstituted pyrrolyl group or a substituted or unsubstitutedpyrrolyl-like group, which process comprises (i) reacting a metal sourcecompound selected from a substituted or unsubstituted cyclopentadienylhalide metal compound, a substituted or unsubstitutedcyclopentadienyl-like halide metal compound, a substituted orunsubstituted pentadienyl halide metal compound, a substituted orunsubstituted pentadienyl-like halide metal compound, a substituted orunsubstituted pyrrolyl halide metal compound or a substituted orunsubstituted pyrrolyl-like halide metal compound, with a base materialin the presence of a solvent and under reaction conditions sufficient toproduce a reaction mixture comprising said organometallic compound, and(ii) separating said organometallic compound from said reaction mixture.The organometallic compound yield resulting from the process of thisinvention can be 60% or greater, preferably 75% or greater, and morepreferably 90% or greater.

This invention further relates in part to a method for producing a film,coating or powder by decomposing an organometallic compound representedby the formula LML′ wherein M is a metal or metalloid, L is asubstituted or unsubstituted cyclopentadienyl group, a substituted orunsubstituted cyclopentadienyl-like group, a substituted orunsubstituted pentadienyl group, a substituted or unsubstitutedpentadienyl-like group, a substituted or unsubstituted pyrrolyl group ora substituted or unsubstituted pyrrolyl-like group, and L′ is asubstituted or unsubstituted pyrrolyl group or a substituted orunsubstituted pyrrolyl-like group, thereby producing the film, coatingor powder. Typically, the decomposing of said organometallic compound isthermal, chemical, photochemical or plasma-activated. Film deposition ispreferably self-limiting and conducted in the presence of at least onereactive gas such as hydrogen.

This invention also relates in part to organometallic mixturescomprising (i) a first organometallic compound represented by theformula LML′ wherein M is a metal or metalloid, L is a substituted orunsubstituted cyclopentadienyl group, a substituted or unsubstitutedcyclopentadienyl-like group, a substituted or unsubstituted pentadienylgroup, a substituted or unsubstituted pentadienyl-like group, asubstituted or unsubstituted pyrrolyl group or a substituted orunsubstituted pyrrolyl-like group, and L′ is a substituted orunsubstituted pyrrolyl group or a substituted or unsubstitutedpyrrolyl-like group, and (ii) one or more different organometalliccompounds (e.g., a hafnium-containing, tantalum-containing ormolybdenum-containing organometallic precursor compound).

This invention relates in particular to depositions involvingpyrrolide-based ruthenium precursors. These precursors can provideadvantages over the other known precursors, especially when utilized intandem with other ‘next-generation’ materials (e.g., hafnium, tantalumand molybdenum). These ruthenium-containing materials can be used for avariety of purposes such as dielectrics, barriers, and electrodes, andin many cases show improved properties (thermal stability, desiredmorphology, less diffusion, lower leakage, less charge trapping, and thelike) than the non-ruthenium containing films.

The invention has several advantages. For example, the method of theinvention is useful in generating organometallic compounds that havevaried chemical structures and physical properties. Films generated fromthe organometallic compounds can be deposited with a short incubationtime, and the films deposited from the organometallic compounds exhibitgood smoothness. These pyrrolyl-containing ruthenium precursors may bedeposited by atomic layer deposition employing a hydrogen reductionpathway in a self-limiting manner, thereby enabling use of ruthenium asa barrier/adhesion layer in conjunction with tantalum nitride in BEOL(back end of line) liner applications. Such pyrrolyl-containingruthenium precursors deposited in a self-limiting manner by atomic layerdeposition may enable conformal film growth over high aspect ratiotrench architectures in a reducing environment.

This invention relates in particular to chemical vapor deposition andatomic layer deposition precursors for next generation devices,specifically pyrrolyl-containing ruthenium precursors that are liquid atroom temperature, i.e., 20° C. The pyrrolyl-containing rutheniumcompounds are preferably hydrogen reducible and deposit in aself-limiting manner.

DETAILED DESCRIPTION OF THE INVENTION

As indicated above, this invention relates in part to organometalliccompounds represented by the formula LML′ wherein M is a metal ormetalloid, L is a substituted or unsubstituted cyclopentadienyl group, asubstituted or unsubstituted cyclopentadienyl-like group, a substitutedor unsubstituted pentadienyl group, a substituted or unsubstitutedpentadienyl-like group, a substituted or unsubstituted pyrrolyl group ora substituted or unsubstituted pyrrolyl-like group, and L′ is asubstituted or unsubstituted pyrrolyl group or a substituted orunsubstituted pyrrolyl-like group.

In a preferred embodiment, this invention relates in part toorganometallic ruthenium compounds selected from

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ and R₁₁ are the same ordifferent and each represents hydrogen, a halogen atom, an acyl grouphaving from 1 to about 12 carbon atoms, an alkoxy group having from 1 toabout 12 carbon atoms, an alkoxycarbonyl group having from 1 to about 12carbon atoms, an alkyl group having from 1 to about 12 carbon atoms, anamine group having from 1 to about 12 carbon atoms or a silyl grouphaving from 0 to about 12 carbon atoms.

Other organometallic compounds within the scope of this invention can berepresented by the formula (L)₂M′L′ or LM′(L′)₂ wherein M′ is alanthanide, L is the same or different and is a substituted orunsubstituted cyclopentadienyl group, a substituted or unsubstitutedcyclopentadienyl-like group, a substituted or unsubstituted pentadienylgroup, a substituted or unsubstituted pentadienyl-like group, asubstituted or unsubstituted pyrrolyl group or a substituted orunsubstituted pyrrolyl-like group, and L′ is the same or different andis a substituted or unsubstituted pyrrolyl group or a substituted orunsubstituted pyrrolyl-like group.

Illustrative substituted cyclopentadienyl-like moieties includecyclo-olefin e.g., cyclohexadienyl, cycloheptadienyl, cyclooctadienylrings, heterocyclic rings, aromatic rings, such as substituted benzenyl,and others, as known in the art. Illustrative substituted orunsubstituted pentadienyl-like groups include linear olefinic groups,e.g., hexadienyl, heptadienyl, octadienyl, and others, as known in theart. Illustrative substituted or unsubstituted pyrrolyl-like groupsinclude pyrrolinyl, pyrazolyl, thiazolyl, oxazolyl, imidazolyl,carbazolyl, triazolyl, indolyl and purinyl.

Permissible substituents of the substituted cyclopentadienyl andcyclopentadienyl-like groups (L), the substituted pentadienyl andpentadienyl-like groups (L) and also the substituted pyrrolyl andpyrrolyl-like groups (L and L′) include halogen atoms, acyl groupshaving from 1 to about 12 carbon atoms, alkoxy groups having from 1 toabout 12 carbon atoms, alkoxycarbonyl groups having from 1 to about 12carbon atoms, alkyl groups having from 1 to about 12 carbon atoms, aminegroups having from 1 to about 12 carbon atoms or silyl groups havingfrom 0 to about 12 carbon atoms.

Illustrative halogen atoms that may be used in R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, R₁₀ and R₁₁ include, for example, fluorine, chlorine,bromine and iodine. Preferred halogen atoms include chlorine andfluorine.

Illustrative acyl groups that may be used in R₁, R₂, R₃, R₄, R₅, R₆, R₇,R₈, R₉, R₁₀ and R₁₁ include, for example, formyl, acetyl, propionyl,butyryl, isobutyryl, valeryl, 1-methylpropylcarbonyl, isovaleryl,pentylcarbonyl, 1-methylbutylcarbonyl, 2-methylbutylcarbonyl,3-methylbutylcarbonyl, 1-ethylpropylcarbonyl, 2-ethylpropylcarbonyl, andthe like. Preferred acyl groups include formyl, acetyl and propionyl.

Illustrative alkoxy groups that may be used in R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, R₁₀ and R₁₁ include, for example, methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy,pentyloxy, 1-methylbutyloxy, 2-methylbutyloxy, 3-methylbutyloxy,1,2-dimethylpropyloxy, hexyloxy, 1-methylpentyloxy, 1-ethylpropyloxy,2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy,1,2-dimethylbutyloxy, 1,3-dimethylbutyloxy, 2,3-dimethylbutyloxy,1,1-dimethylbutyloxy, 2,2-dimethylbutyloxy, 3,3-dimethylbutyloxy, andthe like. Preferred alkoxy groups include methoxy, ethoxy and propoxy.

Illustrative alkoxycarbonyl groups that may be used in R₁, R₂, R₃, R₄,R₅, R₆, R₇, R₈, R₉, R₁₀ and R₁₁ include, for example, methoxycarbonyl,ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl,cyclopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl,sec-butoxycarbonyl, tert-butoxycarbonyl, and the like. Preferredalkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl,propoxycarbonyl, isopropoxycarbonyl and cyclopropoxycarbonyl.

Illustrative alkyl groups that may be used in R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, R₁₀ and R₁₁ include, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl,neopentyl, tert-pentyl, 1-methylbutyl, 2-methylbutyl,1,2-dimethylpropyl, hexyl, isohexyl, 1-methylpentyl, 2-methylpentyl,3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl,2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl,1-ethyl-2-methylpropyl, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, andthe like. Preferred alkyl groups include methyl, ethyl, n-propyl,isopropyl and cyclopropyl.

Illustrative amine groups that may be used in R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, R₁₀ and R₁₁ include, for example, methylamine,dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine,isopropylamine, diisopropylamine, butylamine, dibutylamine,tert-butylamine, di(tert-butyl)amine, ethylmethylamine,butylmethylamine, cyclohexylamine, dicyclohexylamine, and the like.Preferred amine groups include dimethylamine, diethylamine anddiisopropylamine.

Illustrative silyl groups that may be used in R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, R₁₀ and R₁₁ include, for example, silyl, trimethylsilyl,triethylsilyl, tris(trimethylsilyl)methyl, trisilylmethyl, methylsilyland the like. Preferred silyl groups include silyl, trimethylsilyl andtriethylsilyl.

Illustrative organometallic compounds of this invention include, forexample, cyclopentadienylpyrrolylruthenium,methylcyclopentadienylpyrrolylruthenium,ethylcyclopentadienylpyrrolylruthenium,isopropylcyclopentadienylpyrrolylruthenium,tert-butylcyclopentadienylpyrrolylruthenium,methylcyclopentadienyl-2,5-dimethylpyrrolylruthenium,ethylcyclopentadienyl-2,5-dimethylpyrrolylruthenium,isopropylcyclopentadienyl-2,5-dimethylpyrrolylruthenium,tert-butylcyclopentadienyl-2,5-dimethylpyrrolylruthenium,methylcyclopentadienyltetramethylpyrrolylruthenium,ethylcyclopentadienyltetramethylpyrrolylruthenium,isopropylcyclopentadienyltetramethylpyrrolylruthenium,tert-butylcyclopentadienyltetramethylpyrrolylruthenium,1,2-dimethylcyclopentadienylpyrrolylruthenium,1,3-dimethylcyclopentadienylpyrrolylruthenium,1,3-dimethylcyclopentadienyl-2,5-dimethylpyrrolylruthenium,1,3-dimethylcyclopentadienyltetramethylpyrrolylruthenium,pentadienylpyrrolylruthenium, 2,4-dimethylpentadienylpyrrolylruthenium,2,4-dimethylpentadienyl-2,5-dimethylpyrrolylruthenium,2,4-dimethylpentadienyltetramethylpyrrolylruthenium,cyclohexadienylpyrrolylruthenium,cyclohexadienyl-2,5-dimethylpyrrolylruthenium,cyclohexadienyltetramethylpyrrolylruthenium,cycloheptadienylpyrrolylruthenium,cycloheptadienyl-2,5-dimethylpyrrolylruthenium,cycloheptadienyltetramethylpyrrolylruthenium, bis(pyrrolyl)ruthenium,2,5-dimethylpyrrolylpyrrolylruthenium,tetramethylpyrrolylpyrrolylruthenium,bis(2,5-dimethylpyrrolyl)ruthenium,2,5-dimethylpyrrolyltetramethylpyrrolylruthenium, and the like.

With respect to the claimed organometallic compounds of this invention,the following limitations apply: (i) when L and L′ are both fullysubstituted pyrrolyl groups, then at least one of the pyrrolyl groupsubstituents is other than methyl; (ii) when L and L′ are bothsubstituted indolyl groups, then at least one of the indolyl groupsubstituents is other than hydrogen or methyl; (iii) when L is anunsubstituted cyclooctane group and L′ is a substituted pyrrolyl group,then at least one of the pyrrolyl group substituents is other thanmethyl; (iv) when L is an unsubstituted cyclooctane group and L′ is asubstituted indolyl group, then at least one of the indolyl groupsubstituents is other than hydrogen or methyl; and (v) when L is asubstituted cyclohexadiene group and L′ is a substituted pyrrolyl group,then at least one of the pyrrolyl group substituents is other thanmethyl.

As also indicated above, this invention also relates in part to aprocess for the production of an organometallic compound represented bythe formula LML′ wherein M is a metal or metalloid, L is a substitutedor unsubstituted cyclopentadienyl group, a substituted or unsubstitutedcyclopentadienyl-like group, a substituted or unsubstituted pentadienylgroup, a substituted or unsubstituted pentadienyl-like group, asubstituted or unsubstituted pyrrolyl group or a substituted orunsubstituted pyrrolyl-like group, and L′ is a substituted orunsubstituted pyrrolyl group or a substituted or unsubstitutedpyrrolyl-like group, which process comprises (i) reacting a metal sourcecompound selected from a substituted or unsubstituted cyclopentadienylhalide metal, e.g., ruthenium, compound, a substituted or unsubstitutedcyclopentadienyl-like halide metal, e.g., ruthenium, compound, asubstituted or unsubstituted pentadienyl halide metal, e.g., ruthenium,compound, a substituted or unsubstituted pentadienyl-like halide metal,e.g., ruthenium, compound, a substituted or unsubstituted pyrrolylhalide metal, e.g., ruthenium, compound or a substituted orunsubstituted pyrrolyl-like halide metal, e.g., ruthenium, compound,with a base material in the presence of a solvent and under reactionconditions sufficient to produce a reaction mixture comprising saidorganometallic compound, and (ii) separating said organometalliccompound from said reaction mixture. The organometallic compound yieldresulting from the process of this invention can be 60% or greater,preferably 75% or greater, and more preferably 90% or greater.

The process is particularly well-suited for large scale production sinceit can be conducted using the same equipment, some of the same reagentsand process parameters that can easily be adapted to manufacture a widerange of products. The process provides for the synthesis oforganometallic precursor compounds using a process where allmanipulations can be carried out in a single vessel, and which route tothe organometallic precursor compounds does not require the isolation ofan intermediate complex.

The metal source compound starting material may be selected from a widevariety of compounds known in the art. The invention herein most prefersmetals selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe,Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, Si, Ge,a Lanthanide series element or an Actinide series element. Illustrativemetal source compounds include, for example,chlorobis(triphenylphosphine)(ethylcyclopentadienyl)ruthenium,bromobis(triphenylphosphine)(ethylcyclopentadienyl)ruthenium,chlorobis(triisopropylphosphite)(ethylcyclopentadienyl)ruthenium,chlorobis(triethylphosphine)(ethylcyclopentadienyl)ruthenium,chlorobis(triphenylphosphine)(cyclopentadienyl)ruthenium,chlorobis(triphenylphosphine)(methylcyclopentadienyl)ruthenium,chlorobis(triphenylphosphine)(2,4-dimethylpentadienyl)ruthenium,chlorobis(triphenylphosphine)(pyrrolyl)ruthenium,chlorobis(triphenylphosphine)(2,5-dimethylpyrrolyl)ruthenium,chlorobis(triphenylphosphine)(tetramethylpyrrolyl)ruthenium, and thelike.

The process of the invention is preferably useful in generatingorganometallic ruthenium compounds that have varied chemical structuresand physical properties. A wide variety of reaction materials may beemployed in the processes of this invention. For example, in thepreparation of the metal source compounds, ruthenium starting materialsthat may be used include commercial grade Ru(III) chloride hydrate,α-ruthenium(III) chloride, β-ruthenium(III) chloride, ruthenium(III)nitrate, (PPh₃)_(x)RuCl₂ (x=3-4) and the like.

The concentration of the metal source compound starting material canvary over a wide range, and need only be that minimum amount necessaryto react with the base compound and to provide the given metalconcentration desired to be employed and which will furnish the basisfor at least the amount of metal necessary for the organometalliccompounds of this invention. In general, depending on the size of thereaction mixture, metal source compound starting material concentrationsin the range of from about 1 millimole or less to about 10,000millimoles or greater, should be sufficient for most processes.

The base starting material may be selected from a wide variety ofcompounds known in the art. Illustrative bases include any base with apKa greater than about 10, preferably greater than about 20, and morepreferably greater than about 25. The base material is preferablylithium pyrrolides, lithium pentadienides, lithium cyclopentadienides,sodium pyrrolides, sodium pentadienides, sodium cyclopentadienides,bromomagnesium pyrrolides, bromomagnesium pentadienides, bromomagnesiumcyclopentadienides, and the like.

The concentration of the base starting material can vary over a widerange, and need only be that minimum amount necessary to react with themetal source compound starting material. In general, depending on thesize of the first reaction mixture, base starting materialconcentrations in the range of from about 1 millimole or less to about10,000 millimoles or greater, should be sufficient for most processes.

The solvent employed in the method of this invention may be anysaturated and unsaturated hydrocarbons, aromatic hydrocarbons, aromaticheterocycles, alkyl halides, silylated hydrocarbons, ethers, polyethers,thioethers, esters, thioesters, lactones, amides, amines, polyamines,nitriles, silicone oils, other aprotic solvents, or mixtures of one ormore of the above; more preferably, diethylether, pentanes, ordimethoxyethanes; and most preferably hexanes or THF. Any suitablesolvent which does not unduly adversely interfere with the intendedreaction can be employed. Mixtures of one or more different solvents maybe employed if desired. The amount of solvent employed is not criticalto the subject invention and need only be that amount sufficient tosolubilize the reaction components in the reaction mixture. In general,the amount of solvent may range from about 5 percent by weight up toabout 99 percent by weight or more based on the total weight of thereaction mixture starting materials.

Reaction conditions for the reaction of the base compound with the metalsource compound, such as temperature, pressure and contact time, mayalso vary greatly and any suitable combination of such conditions may beemployed herein. The reaction temperature may be the reflux temperatureof any of the aforementioned solvents, and more preferably between about−80° C. to about 150° C., and most preferably between about 20° C. toabout 80° C. Normally the reaction is carried out under ambient pressureand the contact time may vary from a matter of seconds or minutes to afew hours or greater. The reactants can be added to the reaction mixtureor combined in any order. The stir time employed can range from about0.1 to about 400 hours, preferably from about 1 to 75 hours, and morepreferably from about 4 to 16 hours, for all steps.

Other alternative processes that may be used in preparing theorganometallic ruthenium compounds of this invention include thosedisclosed in U.S. Pat. No. 6,605,735 B2 and U.S. Patent ApplicationPublication No. US 2004/0127732 A1, published Jul. 1, 2004, thedisclosure of which is incorporated herein by reference. Theorganometallic compounds of this invention may also be prepared byconventional processes such as described in Legzdins, P. et al. Inorg.Synth. 1990, 28, 196 and references therein.

For organometallic compounds prepared by the method of this invention,purification can occur through recrystallization, more preferablythrough extraction of reaction residue (e.g., hexane) andchromatography, and most preferably through sublimation anddistillation.

Those skilled in the art will recognize that numerous changes may bemade to the method described in detail herein, without departing inscope or spirit from the present invention as more particularly definedin the claims below.

Examples of techniques that can be employed to characterize theorganometallic compounds formed by the synthetic methods described aboveinclude, but are not limited to, analytical gas chromatography, nuclearmagnetic resonance, thermogravimetric analysis, inductively coupledplasma mass spectrometry, differential scanning calorimetry, vaporpressure and viscosity measurements.

Relative vapor pressures, or relative volatility, of organometalliccompound precursors described above can be measured by thermogravimetricanalysis techniques known in the art. Equilibrium vapor pressures alsocan be measured, for example by evacuating all gases from a sealedvessel, after which vapors of the compounds are introduced to the vesseland the pressure is measured as known in the art.

The organometallic compound precursors described herein are preferablyliquid at room temperature, i.e., 20° C., hydrogen reducible, deposit ina self-limiting manner, and are well suited for preparing in-situpowders and coatings. For instance, a liquid organometallic compoundprecursor can be applied to a substrate and then heated to a temperaturesufficient to decompose the precursor, thereby forming a metal or metaloxide coating on the substrate. Applying a liquid precursor to thesubstrate can be by painting, spraying, dipping or by other techniquesknown in the art. Heating can be conducted in an oven, with a heat gun,by electrically heating the substrate, or by other means, as known inthe art. A layered coating can be obtained by applying an organometalliccompound precursor, and heating and decomposing it, thereby forming afirst layer, followed by at least one other coating with the same ordifferent precursors, and heating.

Liquid organometallic compound precursors such as described above alsocan be atomized and sprayed onto a substrate. Atomization and sprayingmeans, such as nozzles, nebulizers and others, that can be employed areknown in the art.

In preferred embodiments of the invention, an organometallic compound,such as described above, is employed in gas phase deposition techniquesfor forming powders, films or coatings. The compound can be employed asa single source precursor or can be used together with one or more otherprecursors, for instance, with vapor generated by heating at least oneother organometallic compound or metal complex. More than oneorganometallic compound precursor, such as described above, also can beemployed in a given process.

As indicated above, this invention relates in part to organometallicmixtures comprising (i) a first organometallic compound represented bythe formula LML′ wherein M is a transition metal, L is a substituted orunsubstituted cyclopentadienyl group, a substituted or unsubstitutedcyclopentadienyl-like group, a substituted or unsubstituted pentadienylgroup, a substituted or unsubstituted pentadienyl-like group, asubstituted or unsubstituted pyrrolyl group or a substituted orunsubstituted pyrrolyl-like group, and L′ is a substituted orunsubstituted pyrrolyl group or a substituted or unsubstitutedpyrrolyl-like group and (ii) one or more different organometalliccompounds (e.g., a hafnium-containing, tantalum-containing ormolybdenum-containing organometallic precursor compound).

Deposition can be conducted in the presence of other gas phasecomponents. In an embodiment of the invention, film deposition isconducted in the presence of at least one non-reactive carrier gas.Examples of non-reactive gases include inert gases, e.g., nitrogen,argon, helium, as well as other gases that do not react with theorganometallic compound precursor under process conditions. In otherembodiments, film deposition is conducted in the presence of at leastone reactive gas. Some of the reactive gases that can be employedinclude but are not limited to hydrazine, oxygen, hydrogen, air,oxygen-enriched air, ozone (O₃), nitrous oxide (N₂O), water vapor,organic vapors, ammonia and others. As known in the art, the presence ofan oxidizing gas, such as, for example, air, oxygen, oxygen-enrichedair, O₃, N₂O or a vapor of an oxidizing organic compound, favors theformation of a metal oxide film.

In an embodiment, hydrogen or another reducing gas may be used in a BEOLatomic layer deposition process at temperatures below 300° C. so thatthe deposition can be carried out in a manner compatible with the restof the BEOL integration strategy. An illustrative atomic layerdeposition strategy for forming BEOL interconnects using ruthenium is asfollows: low K repair, tantalum nitride atomic layer deposition,ruthenium atomic layer deposition and copper electrochemical deposition.Hydrogen reducible ruthenium complexes may also be used for theintegration of ruthenium in MIM stacked cell DRAM capacitors.

In addition to being hydrogen reducible, the ruthenium complexes of thisinvention deposit in a self-limiting manner. For example, in the absenceof a reactant gas, the substrate becomes saturated with a monolayer, orfraction of a monolayer, of the dissociatively chemisorbed rutheniumprecursor. In a self-limiting deposition, only one layer oforganometallic precursor is deposited at a time. Pyrrolyl-containingruthenium precursors deposited in a self-limiting manner by atomic layerdeposition may enable conformal film growth over high aspect ratiotrench architectures in a reducing environment.

As indicated above, this invention also relates in part to a method forproducing a film, coating or powder. The method includes the step ofdecomposing at least one organometallic compound precursor, therebyproducing the film, coating or powder, as further described below.

Deposition methods described herein can be conducted to form a film,powder or coating that includes a single metal or a film, powder orcoating that includes a single metal oxide. Mixed films, powders orcoatings also can be deposited, for instance mixed metal oxide films. Amixed metal oxide film can be formed, for example, by employing severalorganometallic precursors, at least one of which being selected from theorganometallic compounds described above.

Gas phase film deposition can be conducted to form film layers of adesired thickness, for example, in the range of from about 1 nm to over1 mm. The precursors described herein are particularly useful forproducing thin films, e.g., films having a thickness in the range offrom about 10 nm to about 100 nm. Films of this invention, for instance,can be considered for fabricating metal electrodes, in particular asn-channel metal electrodes in logic, as capacitor electrodes for DRAMapplications, and as dielectric materials.

The method also is suited for preparing layered films, wherein at leasttwo of the layers differ in phase or composition. Examples of layeredfilm include metal-insulator-semiconductor, and metal-insulator-metal.

In an embodiment, the invention is directed to a method that includesthe step of decomposing vapor of an organometallic compound precursordescribed above, thermally, chemically, photochemically or by plasmaactivation, thereby forming a film on a substrate. For instance, vaporgenerated by the compound is contacted with a substrate having atemperature sufficient to cause the organometallic compound to decomposeand form a film on the substrate.

The organometallic compound precursors can be employed in chemical vapordeposition or, more specifically, in metalorganic chemical vapordeposition processes known in the art. For instance, the organometalliccompound precursors described above can be used in atmospheric, as wellas in low pressure, chemical vapor deposition processes. The compoundscan be employed in hot wall chemical vapor deposition, a method in whichthe entire reaction chamber is heated, as well as in cold or warm walltype chemical vapor deposition, a technique in which only the substrateis being heated.

The organometallic compound precursors described above also can be usedin plasma or photo-assisted chemical vapor deposition processes, inwhich the energy from a plasma or electromagnetic energy, respectively,is used to activate the chemical vapor deposition precursor. Thecompounds also can be employed in ion-beam, electron-beam assistedchemical vapor deposition processes in which, respectively, an ion beamor electron beam is directed to the substrate to supply energy fordecomposing a chemical vapor deposition precursor. Laser-assistedchemical vapor deposition processes, in which laser light is directed tothe substrate to affect photolytic reactions of the chemical vapordeposition precursor, also can be used.

The method of the invention can be conducted in various chemical vapordeposition reactors, such as, for instance, hot or cold-wall reactors,plasma-assisted, beam-assisted or laser-assisted reactors, as known inthe art.

Examples of substrates that can be coated employing the method of theinvention include solid substrates such as metal substrates, e.g., Al,Ni, Ti, Co, Pt, Ta; metal silicides, e.g., TiSi₂, CoSi₂, NiSi₂;semiconductor materials, e.g., Si, SiGe, GaAs, InP, diamond, GaN, SiC;insulators, e.g., SiO₂, Si₃N₄, HfO₂, Ta₂O₅, Al₂O₃, barium strontiumtitanate (BST); barrier materials, e.g., TiN, TaN; or on substrates thatinclude combinations of materials. In addition, films or coatings can beformed on glass, ceramics, plastics, thermoset polymeric materials, andon other coatings or film layers. In preferred embodiments, filmdeposition is on a substrate used in the manufacture or processing ofelectronic components. In other embodiments, a substrate is employed tosupport a low resistivity conductor deposit that is stable in thepresence of an oxidizer at high temperature or an optically transmittingfilm.

The method of this invention can be conducted to deposit a film on asubstrate that has a smooth, flat surface. In an embodiment, the methodis conducted to deposit a film on a substrate used in wafermanufacturing or processing. For instance, the method can be conductedto deposit a film on patterned substrates that include features such astrenches, holes or vias. Furthermore, the method of the invention alsocan be integrated with other steps in wafer manufacturing or processing,e.g., masking, etching and others.

Chemical vapor deposition films can be deposited to a desired thickness.For example, films formed can be less than 1 micron thick, preferablyless than 500 nanometers and more preferably less than 200 nanometersthick. Films that are less than 50 nanometers thick, for instance, filmsthat have a thickness between about 0.1 and about 20 nanometers, alsocan be produced.

Organometallic compound precursors described above also can be employedin the method of the invention to form films by atomic layer deposition(ALD) or atomic layer nucleation (ALN) techniques, during which asubstrate is exposed to alternate pulses of precursor, oxidizer andinert gas streams. Sequential layer deposition techniques are described,for example, in U.S. Pat. No. 6,287,965 and in U.S. Pat. No. 6,342,277.The disclosures of both patents are incorporated herein by reference intheir entirety.

For example, in one ALD cycle, a substrate is exposed, in step-wisemanner, to: a) an inert gas; b) inert gas carrying precursor vapor; c)inert gas; and d) oxidizer, alone or together with inert gas. Ingeneral, each step can be as short as the equipment will permit (e.g.milliseconds) and as long as the process requires (e.g. several secondsor minutes). The duration of one cycle can be as short as millisecondsand as long as minutes. The cycle is repeated over a period that canrange from a few minutes to hours. Film produced can be a few nanometersthin or thicker, e.g., 1 millimeter (mm).

The method of the invention also can be conducted using supercriticalfluids. Examples of film deposition methods that use supercritical fluidthat are currently known in the art include chemical fluid deposition;supercritical fluid transport-chemical deposition; supercritical fluidchemical deposition; and supercritical immersion deposition.

Chemical fluid deposition processes, for example, are well suited forproducing high purity films and for covering complex surfaces andfilling of high-aspect-ratio features. Chemical fluid deposition isdescribed, for instance, in U.S. Pat. No. 5,789,027. The use ofsupercritical fluids to form films also is described in U.S. Pat. No.6,541,278 B2. The disclosures of these two patents are incorporatedherein by reference in their entirety.

In an embodiment of the invention, a heated patterned substrate isexposed to one or more organometallic compound precursors, in thepresence of a solvent, such as a near critical or supercritical fluid,e.g., near critical or supercritical CO₂. In the case of CO₂, thesolvent fluid is provided at a pressure above about 1000 psig and atemperature of at least about 30° C.

The precursor is decomposed to form a metal film on the substrate. Thereaction also generates organic material from the precursor. The organicmaterial is solubilized by the solvent fluid and easily removed awayfrom the substrate. Metal oxide films also can be formed, for example byusing an oxidizing gas.

In an example, the deposition process is conducted in a reaction chamberthat houses one or more substrates. The substrates are heated to thedesired temperature by heating the entire chamber, for instance, bymeans of a furnace. Vapor of the organometallic compound can beproduced, for example, by applying a vacuum to the chamber. For lowboiling compounds, the chamber can be hot enough to cause vaporizationof the compound. As the vapor contacts the heated substrate surface, itdecomposes and forms a metal or metal oxide film. As described above, anorganometallic compound precursor can be used alone or in combinationwith one or more components, such as, for example, other organometallicprecursors, inert carrier gases or reactive gases.

In a system that can be used in producing films by the method of theinvention, raw materials can be directed to a gas-blending manifold toproduce process gas that is supplied to a deposition reactor, where filmgrowth is conducted. Raw materials include, but are not limited to,carrier gases, reactive gases, purge gases, precursor, etch/clean gases,and others. Precise control of the process gas composition isaccomplished using mass-flow controllers, valves, pressure transducers,and other means, as known in the art. An exhaust manifold can convey gasexiting the deposition reactor, as well as a bypass stream, to a vacuumpump. An abatement system, downstream of the vacuum pump, can be used toremove any hazardous materials from the exhaust gas. The depositionsystem can be equipped with in-situ analysis system, including aresidual gas analyzer, which permits measurement of the process gascomposition. A control and data acquisition system can monitor thevarious process parameters (e.g., temperature, pressure, flow rate,etc.).

The organometallic compound precursors described above can be employedto produce films that include a single metal or a film that includes asingle metal oxide. Mixed films also can be deposited, for instancemixed metal oxide films. Such films are produced, for example, byemploying several organometallic precursors. Metal films also can beformed, for example, by using no carrier gas, vapor or other sources ofoxygen.

Films formed by the methods described herein can be characterized bytechniques known in the art, for instance, by X-ray diffraction, Augerspectroscopy, X-ray photoelectron emission spectroscopy, atomic forcemicroscopy, scanning electron microscopy, and other techniques known inthe art. Resistivity and thermal stability of the films also can bemeasured, by methods known in the art.

In addition to their use in semiconductor applications as chemical vaporor atomic layer deposition precursors for film depositions, theorganometallic compounds of this invention may also be useful, forexample, as catalysts, fuel additives and in organic syntheses.

Various modifications and variations of this invention will be obviousto a worker skilled in the art and it is to be understood that suchmodifications and variations are to be included within the purview ofthis application and the spirit and scope of the claims.

Example 1

A dry 500 milliliter 3-neck round-bottom flask was equipped with acondenser (with at flow through adaptor at the top) and charged with astir bar. The flask was clamped in a fume hood resting on a heatingmantle (attached to a variac) above a stir plate. To the flask was addedchlorobis(triphenylphosphine)-(ethylcyclopentadienyl)ruthenium (14.8grams, 0.020 mol), and the system was purged with nitrogen for 15minutes. After purging the flask was capped with a glass stopper and aseptum, and a slow nitrogen flow was established through the t adaptoron top of the condenser vented to an oil bubbler. Via cannula, anhydroustoluene (150 milliliters) was added and stirring commenced. A THF (50milliliters) solution of lithium pyrrolide (1.6 grams, 0.022 mol) wastransferred to the toluene suspension via cannula. The brown solutionwas heated to gentle reflux and stirred for 16 hours. After cooling toroom temperature, the solvent was removed under reduced pressure. Theresulting residue was agitated in hexanes (4×100 milliliters) andfiltered through a medium porosity frit. The hexanes were removed fromthe yellow filtrate under reduced pressure, and the resulting darkyellow liquid was vacuum distilled (approximately 0.3 torr) through ashort path distillation head. Product collection occurred atapproximately 100° C. The yellow liquid collected was characterized byNMR and GC-MS. MS (M+, relative intensity): 260 (100), 246 (40), 193(33), 167 (9). ¹H NMR (300 MHz, toluene-d₈, δ): 5.64 (t, α-pyrrolyl, J=1Hz), 4.62 (t, β-pyrrolyl, J=1 Hz), 4.38 (t, Cp, J=2 Hz), 4.30 (t, Cp,J=2 Hz), 2.04 (q, CH₂, J=8), 1.02 (t, CH₃, J=8). The product isethylcyclopentadienylpyrrolylruthenium represented by the structurebelow.

Example 2

Lithium 2,5-dimethylpyrrolide was synthesized separately by standardlithiation techniques utilizing n-butyllithium and 2,5-dimethylpyrrolein hexanes. Within a dry nitrogen atmosphere glove box a dry, one-neck 1liter round-bottom flask with an airfree Teflon valve was charged with astir bar. To the flask was added lithium 2,5-dimethylpyrrolide (6.0grams, 0.059 mol), anhydrous THF (75 milliliters) and anhydrous hexanes(300 milliliters). Tris(triphenylphosphine)-dichlororuthenium (14.3grams, 0.015 mol) was added. The flask was capped, removed from theglove box, fitted with a condenser under a nitrogen purge, and refluxedunder nitrogen (with stirring) in a fume hood (14 hours). After coolingto room temperature, the solvent was removed under reduced pressure, andthe residue was returned to the glove box. The crude material wasagitated with hexanes, then filtered through a medium porosity frit. Thefiltrate was reduced to about 10 milliliters, then loaded on to a silicagel column. Elution with anhydrous diethylether removed the remainingtriphenylphosphine. Elution with anhydrous THF produced a bright yellowband, which was collected, and the THF was removed to yield a lightyellow/beige solid. The pure compound,bis(2,5-dimethylpyrrolyl)ruthenium, was thermally stable in a drynitrogen atmosphere. GC/MS (M+, relative intensity): 289 (100), 193(26). ¹H NMR (300 MHz, C₆D₆, δ): 4.45 (s, β-pyrrolyl, 2H), 2.11 (s, CH₃,6H). DSC: mp=73° C.

1. A process for the production of an organometallic compound selectedfrom

wherein R₁, R₂, R₃ and R₄ each represent hydrogen, R₅, R₆, R₇, R₈ and R₉are the same or different and each represents hydrogen, a halogen atom,an acyl group having from 1 to about 12 carbon atoms, an alkoxy grouphaving from 1 to about 12 carbon atoms, an alkoxycarbonyl group havingfrom 1 to about 12 carbon atoms, an alkyl group having from 1 to about12 carbon atoms, an amine group having from 1 to about 12 carbon atomsor a silyl group having from 0 to about 12 carbon atoms; and whereinsaid organometallic compound is a liquid at 20° C. and atmosphericpressure; which process comprises (i) reacting a ruthenium sourcecompound selected from a substituted or unsubstituted cyclopentadienylhalide ruthenium compound or a substituted or unsubstituted pyrrolylhalide ruthenium compound, with a base material in the presence of asolvent and under reaction conditions sufficient to produce a reactionmixture comprising said organometallic compound, and (ii) separatingsaid organometallic compound from said reaction mixture.
 2. A processfor the production of an organometallic compound represented by theformula LML′ wherein M is ruthenium, L is a substituted or unsubstitutedcyclopentadienyl group, and L′ is an unsubstituted pyrrolyl group,wherein said organometallic compound is a liquid at 20° C. andatmospheric pressure; which process comprises (i) reacting a rutheniumsource compound selected from a substituted or unsubstitutedcyclopentadienyl halide ruthenium compound or an unsubstituted pyrrolylhalide ruthenium compound, with a base material in the presence of asolvent and under reaction conditions sufficient to produce a reactionmixture comprising said organometallic compound, and (ii) separatingsaid organometallic compound from said reaction mixture.
 3. The processof claim 1 wherein the organometallic compound is selected fromcyclopentadienylpyrrolylruthenium,methylcyclopentadienylpyrrolylruthenium,ethylcyclopentadienylpyrrolylruthenium,isopropylcyclopentadienylpyrrolylruthenium,tert-butylcyclopentadienylpyrrolylruthenium,1,2-dimethylcyclopentadienylpyrrolylruthenium, and1,3-dimethylcyclopentadienylpyrrolylruthenium.
 4. A process for theproduction of an organometallic compound selected from

wherein R₁, R₂, R₃ and R₄ each represent hydrogen, R₅, R₆, R₇, R₈ and R₉are the same or different and each represents hydrogen or an alkyl grouphaving from 1 to about 12 carbon atoms; and wherein said organometalliccompound is a liquid at 20° C. and atmospheric pressure; which processcomprises (i) reacting a ruthenium source compound selected from asubstituted or unsubstituted cyclopentadienyl halide ruthenium compoundor a substituted or unsubstituted pyrrolyl halide ruthenium compound,with a base material in the presence of a solvent and under reactionconditions sufficient to produce a reaction mixture comprising saidorganometallic compound, and (ii) separating said organometalliccompound from said reaction mixture.
 5. A process for the production ofan organometallic compound represented by the formula LML′ wherein M isruthenium, L is a substituted or unsubstituted cyclopentadienyl group,wherein said substituted cyclopentadienyl group is substituted with oneor more alkyl groups having from 1 to about 12 carbon atoms, and L′ isan unsubstituted pyrrolyl group; wherein said organometallic compound isa liquid at 20° C. and atmospheric pressure; which process comprises (i)reacting a ruthenium source compound selected from a substituted orunsubstituted cyclopentadienyl halide ruthenium compound or anunsubstituted pyrrolyl halide ruthenium compound, with a base materialin the presence of a solvent and under reaction conditions sufficient toproduce a reaction mixture comprising said organometallic compound, and(ii) separating said organometallic compound from said reaction mixture.6. The process of claim 5 wherein the organometallic compound isselected from cyclopentadienylpyrrolylruthenium,methylcyclopentadienylpyrrolylruthenium,ethylcyclopentadienylpyrrolylruthenium,isopropylcyclopentadienylpyrrolylruthenium,tert-butylcyclopentadienylpyrrolylruthenium,1,2-dimethylcyclopentadienylpyrrolylruthenium, and1,3-dimethylcyclopentadienylpyrrolylruthenium.
 7. A process for theproduction of an organometallic compound represented by the formula

wherein R₁, R₂, R₃ and R₄ each represent hydrogen, R₅, R₆, R₇, R₈ and R₉are the same or different and each represents hydrogen, a halogen atom,an acyl group having from 1 to about 12 carbon atoms, an alkoxy grouphaving from 1 to about 12 carbon atoms, an alkoxycarbonyl group havingfrom 1 to about 12 carbon atoms, an alkyl group having from 1 to about12 carbon atoms, an amine group having from 1 to about 12 carbon atomsor a silyl group having from 0 to about 12 carbon atoms; and whereinsaid organometallic compound is a liquid at 20° C. and atmosphericpressure; which process comprises (i) reacting a ruthenium sourcecompound selected from a substituted or unsubstituted cyclopentadienylhalide ruthenium compound or an unsubstituted pyrrolyl halide rutheniumcompound, with a base material in the presence of a solvent and underreaction conditions sufficient to produce a reaction mixture comprisingsaid organometallic compound, and (ii) separating said organometalliccompound from said reaction mixture.
 8. A process for the production ofan organometallic compound represented by the formula

wherein R₁, R₂, R₃ and R₄ each represent hydrogen, R₅, R₆, R₇, R₈ and R₉are the same or different and each represents hydrogen or an alkyl grouphaving from 1 to about 12 carbon atoms, provided at least one of R₅, R₆,R₇, R₈ and R₉ is hydrogen; and wherein said organometallic compound is aliquid at 20° C. and atmospheric pressure; which process comprises (i)reacting a ruthenium source compound selected from a substituted orunsubstituted cyclopentadienyl halide ruthenium compound or anunsubstituted pyrrolyl halide ruthenium compound, with a base materialin the presence of a solvent and under reaction conditions sufficient toproduce a reaction mixture comprising said organometallic compound, and(ii) separating said organometallic compound from said reaction mixture.